CN102746406B - Silane-modified cationized cellulose - Google Patents
Silane-modified cationized cellulose Download PDFInfo
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Abstract
A method of producing silane-modified cationized cellulose that has excellent aqueous dispersibility, including: a step (1) of cationizing water-soluble cellulose ether in a presence of alkali in a mixed solvent of a water-compatible organic solvent and water to obtain slurry comprising cationized cellulose,a step (2) of adding acid to said slurry and neutralizing said alkali,a step (3) of reacting said cationized cellulose obtained after said neutralization with an amino silane compound which is 0.3-10% by mass relative to an amount of water-soluble cellulose ether used in step (1),and a step (4) of drying the obtained slurry, wherein: drying is conducted in step (4) at 115-160 DEG C until weight loss on drying is 5% by weight or less, or there is also including a step (5) of adding a water-compatible organic solvent or a mixed solvent of a water-compatible organic solvent and water to the cationized cellulose after the neutralization so that water content in a whole solvent that contacts the cationized cellulose is 10% by mass or less.
Description
The application is the divisional application of following application.
Denomination of invention: the preparation method of silane-modified cationized cellulose
The applying date: on August 22nd, 2008
Application number: 200880103518.0 (PCT/JP2008/065002)
Technical field
The present invention relates to the preparation method of silane-modified cationized cellulose, and by silane-modified cationized cellulose that above-mentioned preparation method manufactures.
The patent application 2007-216089 CLAIM OF PRIORITY that the application filed an application to Japan according on August 22nd, 2007, quotes its content.
Background technology
The water-soluble cellulose ether of hydroxy alkyl cellulose etc., owing to having wetting ability, thickening property, is therefore widely used in various fields such as thickening material, tackiness agent, dispersion agent, emulsion stabilizers.
In these purposes, water-soluble cellulose ether is generally dissolved in water or moisture the solvent mixture (hereinafter sometimes referred to " water solvent ") uses afterwards, therefore, considers solvability, is usually made as microgranular use.
But this kind of particulate water-soluble cellulose ether, because the solvability for water or water solvent is very high, when therefore directly dropping into water or water solvent, dissolve after only water is moistened on the surface of each particle, adhere to into block between particle, generate so-called doughball (マ マ ュ).Once generate this doughball, because the contact area of water-soluble cellulose ether and water extremely reduces, therefore dissolving water-soluble cellulose ether completely needs spended time, and industrial procedure has problems.
For this kind of problem, known having is carried out processing to water-soluble cellulose ether oxalic dialdehyde, improves hydrophobicity, improves the oxalic dialdehyde process of water dispersible.By oxalic dialdehyde process, oxalic dialdehyde is with the hydroxyl reaction of water-soluble cellulose ether, and by hemiacetal linkage, oxalic dialdehyde is cross-linked with water-soluble cellulose ether.Because this crosslinked meeting be hydrolyzed due to alkali or heat, the water-soluble cellulose ether therefore through oxalic dialdehyde process can disperse due to the water dispersible of excellence at input water or water solvent, then reveals excellent solvability by alkali or hot body.
But oxalic dialdehyde process, owing to specifying oxalic dialdehyde as change heterology material, therefore requires its substitute technology.
As the substitute technology of oxalic dialdehyde process, there is the silane-modified method proposing to employ silane compound.As silane-modified method, such as, there are the method (patent documentation 1,2) proposing to use aminosilane or epoxy silane, the method (patent documentation 3 ~ 6) etc. using alkyltrialkoxysilaneand, alkyl four acyl group silicol, tetraalkoxysilane, four acyl group silicols.
On the other hand, by water-soluble cellulose ether cationization, be formed as Poise C-80M.As the manufacture method of Poise C-80M, the method (patent documentation 7) that known having makes water-soluble cellulose ether and cationic agent react in the presence of a base.Above-mentioned Poise C-80M is mainly widely used the wetting Agent for Printing Inks (ュ Application デ イ シ ョ ニ Application グ drug) etc. in shampoo, bathing agents.
Patent documentation 1: Japanese Patent examined patent publication 51-2103 publication
Patent documentation 2: Japanese Patent Laid-Open No. Sho 47-35073 publication
Patent documentation 3: Japanese Patent Laid-fair 6-39481 publication
Patent documentation 4: Japanese Patent Laid-Open 8-183801 publication
Patent documentation 5: Japanese Patent Laid-Open 2004-155805 publication
Patent documentation 6: Japanese Patent Laid-Open No. Sho 61-195138 publication
Patent documentation 7: Japanese Patent Laid-Open 2005-171089 publication
Summary of the invention
Poise C-80M is because wetting ability is higher than water-soluble cellulose ether, and therefore water dispersible is poorer.Therefore, for Poise C-80M, also can consider the same with water-soluble cellulose ether, by silane-modified method, Poise C-80M be processed.
But, according to the research of the present inventors, even if the traditional silane-modified method being used for water-soluble cellulose ether to be used for the modification of Poise C-80M, the dispersiveness for water or water solvent of the silane-modified cationized cellulose obtained sometimes insufficient, to produce a lot of dissolvings remaining.
The present invention in view of the foregoing, the preparation method that object is to provide the silane-modified cationized cellulose that can manufacture water dispersible excellence and the silane-modified cationized cellulose manufactured by above-mentioned preparation method.
The present inventors finds after repeatedly attentively studying, at least before enforcement silane treatment, under using aqueous phase solubleness organic solvent that this Poise C-80M is placed in the solvent environment of amount of moisture below certain value, then use a certain amount of amino silane compounds to carry out silane treatment, thus solve above-mentioned problem.In addition, even if when not carrying out above-mentioned moisture adjustment operation, making loss on drying reach below certain proportion by being dried at the temperature of 115 ~ 160 DEG C after silane treatment, above-mentioned problem can be solved, thus complete the present invention.
The first form of the present invention solving above-mentioned problem is the preparation method containing following operation (1) ~ (4) or the silane-modified cationized cellulose also containing following operation (5).
Operation (1): in the solvent mixture of aqueous phase solubleness organic solvent and water, make water-soluble cellulose ether cationization in the presence of a base, obtain the slurry containing Poise C-80M.
Operation (2): add acid in the slurry that above-mentioned operation (1) obtains, the operation of neutralization bases.
Operation (3): the operation that the above-mentioned Poise C-80M making above-mentioned operation (2) obtain reacts with the amino silane compounds of 0.3 ~ 10 quality % of the water-soluble cellulose ether amount of the raw material as above-mentioned Poise C-80M.
Operation (4): the resultant drying above-mentioned operation (3) be obtained by reacting is the operation of powder, when not implementing following operation (5), is dried to the operation that loss on drying reaches below 5 quality % at the temperature of 115 ~ 160 DEG C.
Operation (5): to the Poise C-80M obtained in above-mentioned operation (2), add the solvent mixture of aqueous phase solubleness organic solvent or aqueous phase solubleness organic solvent and water, with the operation making the moisture in whole solvents of contacting with this Poise C-80M reach below 10 quality %.
Second form of the present invention is the silane-modified cationized cellulose manufactured by the preparation method of the silane-modified cationized cellulose of above-mentioned first form.
By the preparation method of silane-modified cationized cellulose of the present invention, the silane-modified cationized cellulose of water dispersible excellence can be manufactured.
Embodiment
" preparation method of silane-modified cationized cellulose "
The preparation method of the first form of the present invention, containing above-mentioned operation (1) ~ (4), or also containing operation (5).Below illustrate in greater detail each operation.
< operation (1) >
In operation (1), in the solvent mixture of aqueous phase solubleness organic solvent and water, make water-soluble cellulose ether cationization in the presence of a base, obtain the slurry containing Poise C-80M.
As water-soluble cellulose ether, hydroxyalkyl cellulose ether can be enumerated.Hydroxyalkyl cellulose ether is the material of the hydroxyalkyl being combined with alternatively base on cellulosic hydroxyl.
Above-mentioned hydroxyalkyl is with general formula-(A-O)
nthe group that H represents.In formula, A is the alkylidene group of carbonatoms 2 ~ 3, preferred vinyl or propenyl, more preferably vinyl.N is the average addition mole number of alkylene oxide, and above-mentioned average addition mole number, relative to the glucosyl residue (unit skeleton) 1 mole of water-soluble cellulose ether, is preferably 0.5 ~ 3.5 mole, more preferably 1 ~ 2.5 mole.
Hydroxyalkyl cellulose ether also can have the substituting group beyond hydroxyalkyl.As above-mentioned substituting group, the alkyl etc. of such as carbonatoms 1 ~ 3 can be enumerated.
As hydroxyalkyl cellulose ether, Natvosol (HEC), hydroxypropylcellulose (HPC), methyl-hydroxyethyl Mierocrystalline cellulose (MHEC), methyl-hydroxypropyl cellulose element (MHPC), ethyl-Natvosol (EHEC) etc. specifically can be enumerated.Wherein, HEC is cheap, is generally used for the purposes such as thickening material, therefore ideal.These all can use a kind, also can two or more also use.
The hydroxyalkyl cellulose ether related to, can use market sale, also can to synthesize.Mierocrystalline cellulose, by such as, is carried out alkaline purification and becomes soda cellulose, synthesized in it and alkylene oxide reaction by hydroxyalkyl cellulose ether.
As market sale product, HEC ダ イ セ Le SE550, SE600, SE900 etc. that HEC AL-15, AH-15, AX-15, SW-25F, SW-25F, SG-25F, SY-25F and ダ ィ セ Le chemical industry having Sumitomo to refine manufacture manufactures.
As the viscosity of water-soluble cellulose ether, the viscosity in 20 DEG C of the aqueous solution of preferred 2 quality % is 5 ~ 35,000Pas.Viscosity refers to by the viscosity of Brookfield viscometer from measuring after 1 minute.
As aqueous phase solubleness organic solvent, as long as become homogeneous solution when mixing with water, such as, the alcohol of carbonatoms 1 ~ 4, acetone etc. can be enumerated.Wherein, the alcohol of preferred carbonatoms 1 ~ 4, specifically can enumerate, methyl alcohol, ethanol, Virahol, n-propyl alcohol, the trimethyl carbinol etc.Wherein, based on price secutity aspect, preferred alcohol, Virahol, the trimethyl carbinol.
The ratio of the water in mixed solvent, based on the viewpoint suppressing side reaction, make positive ionization more effectively carry out, preferably 12 ~ 30 quality %, more preferably 12 ~ 20 quality %.By more than lower limit, positive ionization can be made more effectively to carry out.More than the upper limit, the Poise C-80M of generation or water-soluble cellulose ether can dissolve, qualification rate reduces, and can form gelation owing to being partially dissolved in water, therefore undesirable in operation, manufacturing.
The usage quantity of mixed solvent, based on avoiding the cationization of water-soluble cellulose ether carrying out in local, and based on improving the viewpoint of volumetric efficiency of reactor, relative to water-soluble cellulose ether 100 mass parts, be preferably 200 ~ 1500 mass parts, more preferably 300 ~ 800 mass parts.
As alkali, the alkali metal hydroxide of sodium hydroxide, potassium hydroxide, lithium hydroxide etc. can be enumerated.Wherein, due to cheap, preferred sodium hydroxide.
The usage quantity of alkali, preferably relative to water-soluble cellulose ether, makes the content of alkali be the amount of 0.1 ~ 10 quality %.
The cationization of water-soluble cellulose ether, can be reacted by water-soluble cellulose ether and cationic agent and be implemented.
As cationic agent, as long as the hydrogen atom of the hydroxyl with water-soluble cellulose ether (active hydrogen) reacts, give water-soluble cellulose ether with the material of cationic, specifically can enumerate, the Racemic glycidol trialkyl ammonium halide of glycidyl trimethylammonium chloride, Racemic glycidol triethyl ammonium chloride, Racemic glycidol trimethylammonium bromide, Racemic glycidol triethylammonium bromide etc.; The halogenated ammonium compound of dimethyl diallyl ammonium chloride, methacryloyl hydroxyvinyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride etc.Wherein, based on cheap, reactive high viewpoint, preferred glycidyl trimethylammonium chloride.
The usage quantity of cationic agent, based on improving the yield of Poise C-80M and avoiding lacking effect, the uneconomic viewpoint corresponding to usage quantity, be preferably the amount of 0.1 ~ 1.4 mole relative to each glucosyl residue unit skeleton in water-soluble cellulose ether, be more preferably the amount of 0.3 ~ 1.2 mole.
The reaction of water-soluble cellulose ether and cationic agent, such as, by after being mixed with above-mentioned mixed solvent and alkali by water-soluble cellulose ether, stirring, add cationic agent, the temperature of reaction being set to regulation is implemented.
Temperature of reaction now, based on promote reaction, Reaction time shorten viewpoint and avoid reacting the viewpoint of sharply carrying out, usually in the scope of 40 ~ 60 DEG C, preferably 45 ~ 55 DEG C.
Reaction times is different according to temperature of reaction, therefore can not determine without exception, but be generally 2 ~ 4 hours.
So can obtain the slurry containing Poise C-80M.
The cation ionization degree of above-mentioned Poise C-80M is not particularly limited, and suitably can select according to the application target of the silane-modified cationized cellulose finally obtained.Be preferably 0.3 ~ 2.5 quality %, more preferably 0.5 ~ 2.0 quality %.Above-mentioned cation ionization degree is at more than 0.3 quality %, and the cationic of above-mentioned Poise C-80M and then the cationic of silane-modified cationized cellulose finally obtained can improve, and its function (thickening property etc.) can promote.At below 2.5 quality %, good with the reactivity of amino silane compounds, the water dispersible of silane-modified cationized cellulose also can promote.
Here, the cation ionization degree of Poise C-80M, refers to the nitrogen-atoms ratio of each glucosyl residue unit skeleton of above-mentioned Poise C-80M.The method that cation ionization degree is recorded by chlorination O-[2-hydroxyl-3-(trimethyl ammonium) propyl group] the Natvosol page of medicine part outer article raw material specification 2006 (Yao Shi newspaper office) measures.Above-mentioned nitrogen-atoms is from cationic agent, and cation ionization degree regulates by regulating the usage quantity etc. of cationic agent.
< operation (2) >
In operation (2), in the slurry that above-mentioned operation (1) obtains, add acid, neutralization bases.
As acid, the such as strong acid of sulfuric acid, hydrochloric acid, nitric acid etc. and the weak acid of acetic acid, phosphoric acid etc. can be enumerated.Wherein, for cheap, preferred hydrochloric acid, sulfuric acid, nitric acid.
The usage quantity of acid, makes the pH of the aqueous solution of final silane-modified cationized cellulose in the scope of expectation described later as long as be suitably adjusted to.The amino silane compounds used due to operation (3) is alkalescence, and therefore its amount preferably makes the amount of pH lower than the pH of above-mentioned expectation of the slurry after the above-mentioned acid of interpolation.Particularly, the pH adding the slurry after above-mentioned acid preferably becomes the amount of 2.0 ~ 6.0 under 25 DEG C of conditions, is more preferably the amount of 3.5 ~ 5.5.Above-mentioned pH is in above-mentioned scope, and the water dispersible of the silane-modified cationized cellulose finally obtained is good, water-soluble also good.
< operation (3) >
In operation (3), the above-mentioned Poise C-80M making above-mentioned operation (2) obtain reacts with the amino silane compounds of 0.3 ~ 10 quality % of the water-soluble cellulose ether amount as above-mentioned Poise C-80M raw material.By making the amino silane compounds of Poise C-80M and afore mentioned rules amount react, effect of the present invention can be obtained.
As amino silane compounds, can enumerate such as, 3-TSL 8330, APTES, 3-amino propyl methyl dimethoxysilane, 3-methacrylamidopropyltrimethylammonium Ethoxysilane, N-2-amino-ethyl-3-TSL 8330, N-2-amino-ethyl-APTES, 3-aminopropyldiethoxy silane, 4-aminobutyl methyldiethoxysilane, N-2-carbonyl ethoxyethyl group-APTES etc.
Wherein, based on free etc. the angle that can not produce methyl alcohol when the silane-modified cationized cellulose finally obtained being used for shampoo or bathing agents etc., preferred APTES, N-2-amino-ethyl-APTES, 3-methacrylamidopropyltrimethylammonium Ethoxysilane, 3-aminopropyldiethoxy silane, 4-aminobutyl methyldiethoxysilane, N-2-carbonyl ethoxyethyl group-APTES.As amino silane compounds, the market sale product of the AY43-059 that KBE-903, the KBE-603 that SHIN-ETSU HANTOTAI's chemical industry can be utilized to manufacture, KBE-9103, eastern レ ダ ゥ コ mono-ニ Application グ manufacture etc.
The usage quantity of amino silane compounds is 0.3 ~ 10 quality % being used as the water-soluble cellulose ether amount of the raw material of Poise C-80M reacted with this amino silane compounds, preferably 0.5 ~ 10 quality %, more preferably 0.9 ~ 5 quality %, further preferred 0.9 ~ 3 quality %.In addition, when not implementing operation described later (5), the usage quantity of preferred amino silane compounds is slightly many, more preferably 1 quality % ~ 8 quality %, further preferred 2 quality % ~ 5 quality %.The usage quantity of above-mentioned silane compound is at more than 0.3 quality %, and water dispersible is good, and within 10 quality %, water dispersible is good, and the effective ingredient amount of Poise C-80M is high, also controllable costs, therefore also ideal in industrial aspect.
As the method making Poise C-80M and amino silane compounds react (silane treatment method), there is no particular restriction, according to object, can use traditional silane treatment method.But, when implementing operation (5), Poise C-80M must be made not contact with the solvent (ratio of water, water is at the mixed solvent etc. of more than 10 quality %) of moisture more than 10 quality % and carry out silane treatment after operation (5).
As the Poise C-80M of the reaction for operation (3), can directly use obtain in operation (2) containing the slurry of Poise C-80M after neutralization, also can use the slurry that operation (2) obtains taken off liquid, remove portion or all solvent, become the material after cake block (ケ mono-キ) or dry product.In addition, in operation (5), the moisture in solvent directly can be used at the slurry of below 10 quality % or cake block, also can use the part or all of solvent eliminating above-mentioned slurry or cake block, the material becoming cake block or dry product.
The de-liquid method of the slurry that operation (2) obtains is not particularly limited, and can utilize the solid-liquid separating method that filtration or centrifugation etc. are conventionally known.Such as can use filter cloth, use centrifugal detachment machine to implement.The de-liquid process solids component preferably proceeded in cake block becomes 30 ~ 80 quality %.
As preferred silane treatment method, can enumerate and the method that amino silane compounds makes it to react rear drying is added to the slurry of above-mentioned Poise C-80M; To cake block or dry product, add with spraying amino silane compounds such as atomizers, react rear dry method.Now, in order to carry out uniform silane treatment, preferably stir after interpolation amino silane compounds.
In silane treatment, there is no particular restriction for temperature of reaction when making Poise C-80M and amino silane compounds react, and suitably can select according to object.Preferably 20 ~ 80 DEG C, more preferably 25 ~ 75 DEG C, preferably 30 ~ 70 DEG C further.Said temperature is more than 20 DEG C, and reaction can fully be carried out, and the water dispersible of the silane-modified cationized cellulose obtained is good, and below 80 DEG C, the tone of above-mentioned silane-modified cationized cellulose is good.
Reaction times, there is no particular restriction, suitably can select according to temperature of reaction, object etc.
Preferably 5 ~ 120 minutes reaction times, more preferably 10 ~ 100 minutes, preferably 15 ~ 80 minutes further.The above-mentioned reaction times, reaction can fully be carried out more than 5 minutes, and the water dispersible of the silane-modified cationized cellulose obtained is good, and within 120 minutes, the tone of above-mentioned silane-modified cationized cellulose is good.
< operation (4) >
In operation (4), the resultant of reaction drying of the Poise C-80M obtain above-mentioned operation (3) and amino silane compounds is powder.
When not implementing following operation (5), the drying in operation (4) is in the temperature of 115 ~ 160 DEG C, make the evaporation such as water, aqueous phase solubleness organic solvent, is dried to loss on drying and reaches below 5 quality %.
Now, drying temperature, higher than 115 DEG C, can obtain fully for dispersiveness, the solvability of water.On the other hand, below 160 DEG C, can be improved dispersed, deliquescent effect, is difficult to appearance painted.Based on the angle obtaining higher effect with a small amount of silane addition, preferably more than 120 DEG C, preferably more than 130 DEG C further.
Drying proceed to above shown in the loss on drying that measures of method below 5 % by weight.
(measuring method of loss on drying)
Loss on drying, 1g (A) is about by measuring dried sample with the weighing bottle (B) of constant in advance, in drying machine at 105 DEG C after dry 2 hours, cover lid on weighing bottle, take out from drying machine, after moisture eliminator lets cool 30 minutes, weigh (C), then tries to achieve according to following formula.
Loss on drying (%)=[A-(C-B)]/A × 100
Above-mentioned loss on drying preferably treatment to 1 less than % by weight, more preferably less than 0.5 % by weight.Loss on drying is fewer, and the dispersiveness for water of the Poise C-80M obtained is better, and dissolution time shortens.In addition, de-liquid process can also be implemented before the drying of operation (4).
De-liquid process, by such as using filter cloth, uses centrifugal liquid remover to carry out.
Reach below 5 quality % to be dried to loss on drying at the temperature of 115 ~ 160 DEG C as above as long as dry, be then not particularly limited, undertaken by known method.
Such as, can at ambient pressure or decompression under, place carry out at the temperature disclosed above.Based on rate of evaporation, the viewpoint preventing thermal degradation when, preferably carry out under decompression, such as, by general used vacuum stirring-up drying machine or oscillatory type vacuum drying machine etc., carry out while stirring under the decompression of 1 ~ 30Torr degree.
In addition, drying temperature when implementing operation (5) is not restricted to above-mentioned statement.About as in powder operation, be preferably dried to loss on drying and reach less than 10 % by weight, more preferably less than 5 % by weight, carry out drying by above-mentioned identical device, method.
< operation (5) >
In the slurry that above-mentioned operation (2) obtains, the moisture used when remaining cationization, the moisture in all solvents in above-mentioned slurry is generally 12 ~ 30 quality %.
In operation (5), to the Poise C-80M after above-mentioned neutralization, add the solvent mixture of aqueous phase solubleness organic solvent or aqueous phase solubleness organic solvent and water, reach below 10 quality % to make the moisture in whole solvents of contacting with this Poise C-80M.Moisture in the whole solvents contacted with this Poise C-80M, based on the viewpoint of dispersed dissolution time, more preferably 2 ~ 7%.
As aqueous phase solubleness organic solvent, the identical aqueous phase solubleness organic solvent enumerated with above-mentioned operation (1) can be enumerated.
Aqueous phase solubleness organic solvent and water very with the ratio of the water in solvent, as long as the moisture that with the addition of in whole solvents (mother liquor) contained in the cake block obtained after the slurry of the Poise C-80M after this mixed solvent or above-mentioned slurry take off liquid process, in the scope of below 10 quality %, suitably can be selected according to the amount of moisture in the slurry of this mixed solvent of interpolation or cake block.
As the implementation method of operation (5), following method (5-1), (5-2) etc. specifically can be enumerated.
Method (5-1): the slurry obtained for above-mentioned operation (2), adds the mixed solvent of aqueous phase solubleness organic solvent or aqueous phase solubleness organic solvent and water, mixing, the method stirred.
Method (5-2): the slurry obtained above-mentioned operation (2), carries out de-liquid process, adds the method for the mixed solvent of aqueous phase solubleness organic solvent or aqueous phase solubleness organic solvent and water in the cake block obtained.
As method (5-2), following method (5-2a), (5-2b) etc. more specifically can be enumerated.
Method (5-2a): after the slurry after the neutralization obtain above-mentioned operation (2) carries out de-liquid, by the cake block obtained in aqueous phase solubleness organic solvent or mixed solvent redispersion, become the method for slurry.
Method (5-2b): after the slurry after the neutralization obtain above-mentioned operation (2) carries out de-liquid, to the method for spray water intermiscibility organic solvent or mixed solvent on the cake block obtained.
When carrying out the process of cake block by spray, also can take cake block to be placed on rotary conveyor etc., the continous treatment process sprayed in the above.
In addition, after these processes, in order to remove aqueous phase solubleness organic solvent or the mixed solvent of use again, also de-liquid process can be carried out.
When method (5-1) and (5-2a), as long as add above-mentioned solvent, reach below 10 quality % to make the moisture that with the addition of in the mother liquor contained by the slurry after the mixed solvent of aqueous phase solubleness organic solvent or aqueous phase solubleness organic solvent and water.
In addition, as method (5-2b) by spray cake block is processed when, can spray, make the moisture in the mother liquor contained by final cake block reach below 10 quality %.
In method (5-2), de-liquid processing method is not particularly limited, and can utilize the solid-liquid separating method that filtration or centrifugation etc. are conventionally known.Such as, by using filter cloth, using centrifugal liquid remover to implement.
De-liquid process preferably makes the solids component in cake block reach 30 ~ 80 quality %.
Above-mentioned solids component amount, be that the cake block of 1g is dry with 105 DEG C, 2 hours, the difference component before and after it calculates.
In addition, the moisture in above-mentioned whole solvent of aqueous phase solubleness organic solvent or mixed solvent, by such as leaving standstill slurry or centrifugation, taking its clarified liq to measure the method for moisture; The slurry that with the addition of after aqueous phase solubleness organic solvent or mixed solvent or cake block are carried out to the confirmations such as the moisture in the liquid after de-liquid process, the de-liquid of mensuration.
Amount of moisture in liquid, by Ka Er-fischer's method, uses the moisture content determining device of market sale, and the determination of trace water device AQV-7 etc. that such as Ping Zhao Industry Co., Ltd manufactures measures.
Containing neutralizing the salt generated in Poise C-80M after above-mentioned neutralization.The process undertaken by aqueous phase solubleness organic solvent or mixed solvent of this operation, also the operation of being undertaken refining by cleaning this salt of removing can be doubled as, but the amount of moisture be used as in the aqueous phase solubleness organic solvent of scavenging solution or mixed solvent is less, in may occurring and the removing decrease in efficiency of salt, in the Poise C-80M that obtains in and salt remain.
Therefore, based in and the viewpoint of removing efficiency of salt, preferably make moisture before the aqueous phase solubleness organic solvent or mixed solvent of below 10 quality % in interpolation, use the aqueous phase solubleness organic solvent of amount of moisture 15 ~ 30 about quality % and the mixed solvent of water separately, Poise C-80M is cleaned (refining).
" silane-modified cationized cellulose "
Silane-modified cationized cellulose of the present invention is by the silane-modified cationized cellulose manufactured by the preparation method of the invention described above.
As the shape of silane-modified cationized cellulose of the present invention, there is no particular restriction, suitably can select according to object.Consider the dispersiveness, solvability etc. to water, preferably Powdered.
Time Powdered, the particle diameter of above-mentioned silane-modified cationized cellulose can consider that application target etc. is suitably selected.Above-mentioned particle diameter preferably 10 ~ 1,000 μm, more preferably 30 ~ 800 μm, preferably 50 ~ 600 μm further.Above-mentioned particle diameter is more than 10 μm, and water dispersible promotes, and in addition, not easily produce dust during use, operability is good.
Above-mentioned particle diameter 1, less than 000 μm, to the favorable solubility of water.
In addition, silane-modified cationized cellulose of the present invention, becomes pH during the 2 quality % aqueous solution, under 25 DEG C of conditions, be preferably 5 ~ 7.5.Above-mentioned pH is below 7.5, and water dispersible promotes, and the words of more than 5 promote the solvability of water.
Silane-modified cationized cellulose of the present invention, as mentioned above, water dispersible is excellent, drops into the water solvent of the mixed solvent of water or water and aqueous phase solubleness organic solvent etc., can easily disperse in the short period of time.In addition, the solvability for water solvent is also excellent.In addition, compare to the Poise C-80M of traditional oxalic dialdehyde process, security aspect is also excellent.Therefore, the wetting Agent for Printing Inks of such as shampoo, bathing agents, cosmetic hair, basic cosmetics, makeup cosmetic, fragrant cosmetic products, Exposure to Sunlight are applied some make up, the purposes on a large scale such as Sun block makeup, manicure preparations, bath apply some make up, wherein very useful as wetting Agent for Printing Inks.
Embodiment
By embodiment, the present invention is further illustrated below, but the present invention there is no and is defined in these embodiments.
In following example, as being not particularly illustrated, " part " and " % " represents mass parts and quality % respectively.
Source chemicals used in following examples and comparative example etc., analytical procedure, evaluation method are as follows.
(1) raw material uses reagent etc.
Natvosol: refine " AH-15L " that manufacture in Sumitomo, purity 80%, 2 quality % solution viscosities (25 DEG C) 1,200mPas).
Virahol: Northeast chemical company manufactures, purity 99.5%.
Sodium hydroxide: Northeast chemical company manufactures.
Glycidyl trimethylammonium chloride: " SY-GTA80 " that this medicine of slope manufactures, effective constituent 73% aqueous solution.
APTES: " KBE-903 " that chemical company of SHIN-ETSU HANTOTAI manufactures, effective constituent 100%.
(2) analytical procedure
Moisture (%) (Ka Er-fischer's method) in (a) solvent
The ratio of the amount of moisture in the whole solvents contacted with the Poise C-80M before silane treatment.For in the clarified liq of embodiment 1 ~ 16, comparative example 1 ~ 9, for embodiment 8 and comparative example 5, refer to the ratio of the amount of moisture in the liquid of the de-liquid before silane treatment.
Use the determination of trace water device AQV-7 that Ping Zhao Industry Co., Ltd manufactures, as sample size, analyze 0.3g.
(b) process silane amount (%)
Calculate according to following formula.
Process silane amount=(B/A) × 100 (%)
[in formula, A is effective addition (total mass (g) × purity (%)) of water-soluble cellulose ether (Natvosol), and B is effective addition (total mass (g) × effectively divide (%)) of silane compound (APTES).]
(c) pH measuring method
The pH meter " PH71 " using Yokogawa Electricity Co., Ltd. to manufacture measures.
(3) evaluation method
Sieve with sieve pulverous silane-modified cationized cellulose that each embodiment and comparative example obtain, using the particle diameter 106 ~ 425 μm that obtains as sample, for following evaluation.
(a) water dispersible
I () be dispersion amount after 2 minutes
Distilled water 50g is added in 100mL beaker, sample 0.5g is dropped into from the At The Height apart from water surface 4cm, sample drops into end after 2 minutes, the ratio (%) that visual valuation powder does not remain in the water surface, is dispersed in water, using this as dispersion amount after 2 minutes.
(ii) complete jitter time
In 100mL beaker, add distilled water 50g, sample 0.5g is dropped into from the At The Height apart from water surface 4cm, to the time that powder is dispersed in water completely after working sample drops into and terminates, using this as complete jitter time.In addition, still do not have fully decentralized through 300 seconds after input, using this as the terminal measured, be evaluated as " more than 300 seconds ".
(b) dissolution time
In 200mL height cylinder beaker (external diameter 6cm), add the distilled water 150g of 25 DEG C, stirred by the agitating vane being arranged on HEIDON ス リ mono-ワ Application モ mono-タ mono-(manufacture of Xin Dong KCC).Agitating vane uses the Scroll-type (2 slurries) of φ 40mm, and the bottom of blade is located at more than the 2cm apart from beaker bottom.Mixing speed is 400rpm.
Add sample 3.5g while stirring, then continue immediately to stir in 70 DEG C of water-baths.Time after visual working sample drops into sample is dissolved as transparent liquid completely.
[embodiment 1]
For Natvosol 50g, load mixed solvent 500g, the 25 quality % aqueous sodium hydroxide solution 7.1g of isopropanol/water (mass ratio)=85/15 at removable flask, be uniformly mixed 30 minutes.Then stop stirring, leaving standstill, the clarified liq 250g of removing mixed solvent.Then the remainder of removable flask is warming up to 50 DEG C, adds glycidyl trimethylammonium chloride 24g as cationic agent, continue at 3 hours, 50 DEG C to stir.Then, add 10 quality % hydrochloric acid aqueous isopropanols, be modulated to pH4.5 (temperature 50 C), obtain Poise C-80M slurry.Then in this slurry, add Virahol (99.5%) 1350g, be uniformly mixed 15 minutes.Then, stop stirring, leaving standstill, remove its clarified liq 1400g.Moisture in this clarified liq is 2%.Then this slurry is heated to 50 DEG C, add APTES 1.2g and mix 45 minutes.Then this slurry centrifuge is taken off liquid, carry out drying under reduced pressure (105 DEG C) 5 hours, obtain target silane-modified cationized cellulose.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 7.0 (temperature 25 DEG C).
[embodiment 2]
Obtain till pH is modulated to the Poise C-80M slurry of 4.5 identical with embodiment 1, in the slurry obtained, add Virahol (99.5%) 550g afterwards, be uniformly mixed 15 minutes.Then, stop stirring, leaving standstill, remove its clarified liq 600g.Moisture in this clarified liq is 7%.Then carry out the process identical with embodiment 1, obtain target silane-modified cationized cellulose.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 6.3 (temperature 25 DEG C).
[embodiment 3]
Except adding APTES 0.2g, by the method identical with embodiment 2, obtain silane-modified cationized cellulose.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 5.6 (temperature 25 DEG C).
[embodiment 4]
Except adding APTES 0.36g, by the method identical with embodiment 2, obtain silane-modified cationized cellulose.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 5.8 (temperature 25 DEG C).
[embodiment 5]
Except adding APTES 0.8g, by the method identical with embodiment 2, obtain silane-modified cationized cellulose.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 6.1 (temperature 25 DEG C).
[embodiment 6]
Except adding APTES 2.0g, by the method identical with embodiment 2, obtain silane-modified cationized cellulose.In and time the pH of slurry be 4.0 (temperature 50 Cs), the pH of 2% aqueous solution of the silane-modified cationized cellulose obtained is 6.6 (temperature 25 DEG C).
[embodiment 7]
Except adding APTES 4.0g, by the method identical with embodiment 2, obtain silane-modified cationized cellulose.In and time the pH of slurry be 2.6 (temperature 50 Cs), the pH of 2% aqueous solution of the silane-modified cationized cellulose obtained is 7.1 (temperature 25 DEG C).
[embodiment 8]
For Natvosol 50g, load mixed solvent 500g, the 25 quality % aqueous sodium hydroxide solution 7.1g of isopropanol/water (mass ratio)=85/15 at removable flask, be uniformly mixed 30 minutes.Then stop stirring, leaving standstill, the clarified liq 250g of removing mixed solvent.Then the remainder of removable flask is warming up to 50 DEG C, adds glycidyl trimethylammonium chloride 24g as cationic agent, continue in 3 hours, 50 DEG C to stir.Then, add 10 quality % hydrochloric acid Virahol ester solutions, be modulated to pH4.5 (temperature 50 C), then this slurry taken off liquid by centrifuge, obtain Poise C-80M cake block.Then, by this cake block redispersion in the mixed solvent 250g of isopropanol/water (mass ratio)=79/21,15 minutes are uniformly mixed.
Then, this slurry is obtained de-liquid by centrifuge.In the cake block obtained, add Virahol (99.5%) 93g, be uniformly mixed 15 minutes, the slurry centrifuge obtained is taken off liquid.The moisture taken off in the liquid of liquid of process is now 7%.To the Poise C-80M cake block spraying APTES 0.5g obtained, after being uniformly mixed, carrying out drying under reduced pressure (105 DEG C) 5 hours, obtain target silane-modified cationized cellulose.
The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 5.6 (temperature 25 DEG C).
[embodiment 9]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH5.8.Moisture in this clarified liq is 19%.Then, this slurry is heated to 50 DEG C, add APTES 1.2g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 125 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[embodiment 10]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH4.5.Moisture in this clarified liq is 20%.Then, this slurry is heated to 50 DEG C, add APTES 4.0g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 125 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[embodiment 11]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH5.8.Moisture in this clarified liq is 19%.Then, this slurry is heated to 50 DEG C, add APTES 0.8g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 135 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[embodiment 12]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH5.2.Moisture in this clarified liq is 19%.Then, this slurry is heated to 50 DEG C, add APTES 2.0g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 135 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[embodiment 13]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH4.7.Moisture in this clarified liq is 20%.Then, this slurry is heated to 50 DEG C, add APTES 3.2g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 135 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[embodiment 14]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH4.5.Moisture in this clarified liq is 20%.Then, this slurry is heated to 50 DEG C, add APTES 4.0g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 135 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[embodiment 15]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH5.8.Moisture in this clarified liq is 19%.Then, this slurry is heated to 50 DEG C, add APTES 0.8g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, carry out 145 DEG C of drying under reduced pressure 5 hours, obtain target cationic cellulose.
[embodiment 16]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH4.5.Moisture in this clarified liq is 20%.Then, this slurry is heated to 50 DEG C, add APTES 4.0g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 145 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[comparative example 1]
After obtaining carrying out till pH is modulated to the Poise C-80M slurry of 4.5, do not carry out the process adding Virahol (99.5%) in the slurry obtained identically with embodiment 1, but direct standing separation, remove its clarified liq 50g.Moisture in this clarified liq is 14%.Then carry out the process identical with embodiment 1, obtain silane-modified cationized cellulose.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 5.9 (temperature 25 DEG C).
[comparative example 2]
After obtaining carrying out till pH is modulated to the Poise C-80M slurry of 4.5 identically with embodiment 1, add distilled water 13g in the slurry and be uniformly mixed 15 minutes.Moisture in this clarified liq is 17%.Then carry out the process identical with embodiment 1, obtain silane-modified cationized cellulose.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 5.7 (temperature 25 DEG C).
[comparative example 3]
After obtaining carrying out till pH is modulated to the Poise C-80M slurry of 4.5 identically with embodiment 1, add distilled water 30g in the slurry and be uniformly mixed 15 minutes.Moisture in this clarified liq is 20%.Then carry out the process identical with embodiment 1, obtain silane-modified cationized cellulose.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 5.3 (temperature 25 DEG C).
[comparative example 4]
Except adding APTES 0.04g, obtain silane-modified cationized cellulose by the method identical with embodiment 2.The pH of 2% aqueous solution of above-mentioned silane-modified cationized cellulose is 5.3 (temperature 25 DEG C).
[comparative example 5]
The slurry centrifuge being modulated to pH4.5 is taken off liquid, obtain Poise C-80M cake block till carry out identically with embodiment 8 after, by the cake block redispersion in the mixed solvent 250g of isopropanol/water (mass ratio)=79/21 obtained, be uniformly mixed 15 minutes.Then this slurry is taken off liquid by centrifuge.The moisture taken off in the liquid of liquid of process is now 20%.To the Poise C-80M cake block spraying APTES 0.5g obtained, after being uniformly mixed, carrying out drying under reduced pressure (105 DEG C) 5 hours, obtain silane-modified cationized cellulose.In and time the pH of slurry be 4.0 (temperature 50 Cs), the pH of 2% aqueous solution of the silane-modified cationized cellulose obtained is 5.6 (temperature 25 DEG C).
[comparative example 6]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH5.6.Moisture in this clarified liq is 19%.Then, this slurry is heated to 50 DEG C, add APTES 1.2g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 100 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[comparative example 7]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH5.6.Moisture in this clarified liq is 19%.Then, this slurry is heated to 50 DEG C, add APTES 1.2g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 115 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[comparative example 8]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH6.0.Moisture in this clarified liq is 19%.Then, this slurry is heated to 50 DEG C, add APTES 0.04g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 145 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
[comparative example 9]
For Natvosol 50g, add the mixed solvent 500g of isopropanol/water (mass ratio)=85/15,25 quality % aqueous sodium hydroxide solution 7.1g, mixing.Then 30 minutes are uniformly mixed, the clarified liq 250g of removing mixed solvent.Then be warming up to 50 DEG C, as cationic agent, add glycidyl trimethylammonium chloride 24g, react 3 hours.Then, add 10 quality % hydrochloric acid IPA solution, obtain the Poise C-80M slurry being modulated to pH6.0.Moisture in this clarified liq is 19%.Then, this slurry is heated to 50 DEG C, add APTES 0.2g, mix 45 minutes.Then this slurry is taken off liquid by centrifuge, at 145 DEG C, drying under reduced pressure 5 hours, obtains target cationic cellulose.
For the silane-modified cationized cellulose that above-described embodiment 1 ~ 16 and comparative example 1 ~ 9 obtain, evaluated by the evaluation method shown in above-mentioned (3).Its result represents in table 1 ~ 2.
[table 1]
As clear and definite in above result institute, the silane-modified cationized cellulose that embodiment 1 ~ 16 obtains, many, the complete jitter times of the dispersion amount after 2 minutes are also short, demonstrate excellent water dispersible.In addition, dissolution time is also short.Process silane amount is that in the embodiment 1 ~ 2,4 ~ 16 of 0.9 ~ 10 quality %, water dispersible is good especially.
On the other hand, the silane-modified cationized cellulose that the moisture in the solvent before silane treatment obtains more than the comparative example 1 ~ 3,5 ~ 9 of 10 quality %, compares to embodiment 1 ~ 8, after 2 minutes, dispersion amount is few, except comparative example 7, complete jitter time is all more than 300 seconds, and water dispersible is poor.In addition, process silane amount be 0.1 quality % relatively in 4 and 8, dispersion amount, the completely all non-constant of jitter time after 2 minutes.In addition, the dissolution time of comparative example 4 is the longest.
Industrial Availability
According to the preparation method of silane-modified cationized cellulose of the present invention, the preparation of the silane-modified cationized cellulose of water dispersible excellence can be realized.
Claims (2)
1. a pulverous silane-modified cationized cellulose, sieves it with sieve, using pulverous silane-modified cationized cellulose of particle diameter 106 ~ 425 μm of obtaining as sample, when carrying out following evaluation,
Complete jitter time is 20 seconds and dissolution time is 6 minutes,
Complete jitter time is 16 seconds and dissolution time is 6 minutes,
Complete jitter time is 41 seconds and dissolution time is 23 minutes,
Complete jitter time is 34 seconds and dissolution time is 15 minutes,
Complete jitter time is 8 seconds and dissolution time is 8 minutes,
Complete jitter time is 10 seconds and dissolution time is 4 minutes,
Complete jitter time is 21 seconds and dissolution time is 9 minutes,
Complete jitter time is 22 seconds and dissolution time is 6 minutes,
Complete jitter time is 17 seconds and dissolution time is 8 minutes,
Complete jitter time is 15 seconds and dissolution time is 9 minutes, or
Complete jitter time is 18 seconds and dissolution time is 8 minutes,
And dispersion amount is 100% after 2 minutes,
Complete jitter time:
Distilled water 50g is added in 100mL beaker, sample 0.5g is dropped into from the At The Height apart from water surface 4cm, to the time that powder is dispersed in water completely after working sample drops into and terminates, using this as complete jitter time, still not fully decentralized through 300 seconds after input, using this as the terminal measured, be evaluated as more than 300 seconds
Dissolution time:
The distilled water 150g of 25 DEG C is added in the 200mL height cylinder beaker of external diameter 6cm, stirred by the agitating vane being arranged on stirrer, agitating vane uses 2 slurries of the Scroll-type of φ 40mm, and the bottom of blade is located at more than the 2cm apart from beaker bottom, mixing speed is 400rpm
Add sample 3.5g while stirring, then continue immediately to stir in 70 DEG C of water-baths, the time after visual working sample drops into sample is dissolved as transparent liquid completely,
Dispersion amount after 2 minutes:
In 100mL beaker, add distilled water 50g, dropped into by sample 0.5g from the At The Height apart from water surface 4cm, sample dropped into end after 2 minutes, the ratio % that visual valuation powder does not remain in the water surface, is dispersed in water, using this as dispersion amount after 2 minutes.
2. a pulverous silane-modified cationized cellulose, is characterized in that, by preparation method's manufacture of following silane-modified cationized cellulose,
The preparation method of described silane-modified cationized cellulose is the preparation method of the silane-modified cationized cellulose of dispersiveness in water and solvability excellence, and this preparation method comprises:
In the solvent mixture of aqueous phase solubleness organic solvent and water, make water-soluble cellulose ether cationization in the presence of a base, obtain the operation (1) of the slurry containing Poise C-80M;
Acid is added, the operation (2) of neutralization bases in the above-mentioned slurry obtained;
Make the operation (3) that the Poise C-80M after the above-mentioned neutralization obtained reacts with the amino silane compounds of 0.3 ~ 10 quality % of the water-soluble cellulose ether amount as above-mentioned Poise C-80M raw material;
By the operation (4) that the resultant drying obtained in the reaction of above-mentioned operation (3) is powder,
Above-mentioned preparation method comprises further: the solvent mixture Poise C-80M obtained in above-mentioned operation (2) being added to aqueous phase solubleness organic solvent or aqueous phase solubleness organic solvent and water, with the operation (5) making the moisture in whole solvents of contacting with this Poise C-80M reach below 10 quality %
When pulverous silane-modified cationized cellulose of the particle diameter 106 ~ 425 μm obtained carrying out sieving with sieve carries out following evaluation as sample, after 2 minutes, dispersion amount is 100%,
Dispersion amount after 2 minutes:
In 100mL beaker, add distilled water 50g, dropped into by sample 0.5g from the At The Height apart from water surface 4cm, sample dropped into end after 2 minutes, the ratio % that visual valuation powder does not remain in the water surface, is dispersed in water, using this as dispersion amount after 2 minutes.
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| WO2010055664A1 (en) * | 2008-11-12 | 2010-05-20 | ライオン株式会社 | Cleanser composition |
| US8981080B2 (en) | 2009-06-04 | 2015-03-17 | Lion Corporation | Silane-modified cationized polymeric compound and process for production thereof |
| UA109772C2 (en) * | 2009-07-02 | 2015-10-12 | AGENT FOR IMPROVING SOIL HYDROPHILITY AND APPLICATION METHODS | |
| JP6136594B2 (en) * | 2013-06-03 | 2017-05-31 | 王子ホールディングス株式会社 | Method for producing fine cellulose fiber |
| CN104086780B (en) * | 2014-07-29 | 2017-02-15 | 广州天赐高新材料股份有限公司 | Polysiloxane-modified cationic polysaccharide compound as well as preparation method and application thereof |
| JP6576456B2 (en) | 2014-11-06 | 2019-09-18 | エフ．ホフマン−ラ ロシュ アーゲーＦ． Ｈｏｆｆｍａｎｎ−Ｌａ Ｒｏｃｈｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ | Fc region variants with modified FcRn binding properties and protein A binding properties |
| CN104861215B (en) * | 2015-06-04 | 2019-02-26 | 中国海洋石油集团有限公司 | A method of improving the dispersing and dissolving performance of oil field biological polyoses |
| CA3003425C (en) * | 2015-10-27 | 2024-01-02 | The Research Foundation For The State University Of New York | Method for preparing modified nanocrystalline cellulose |
| US9820928B1 (en) * | 2016-04-27 | 2017-11-21 | Corn Products Development, Inc. | Modified polysaccharides |
| CN106565906B (en) * | 2016-11-07 | 2019-02-26 | 浙江理工大学 | A kind of preparation method of hydrophobically modified celluloses base flocculation material |
| JP2017133037A (en) * | 2017-04-26 | 2017-08-03 | 王子ホールディングス株式会社 | Fine cellulose fiber production process |
| KR102139350B1 (en) * | 2018-05-30 | 2020-07-29 | 주식회사 엘지생활건강 | Dye-Enhancement Functional Polymer for Shampoo and Detergent Composition Comprising the Same |
| CN113439091A (en) | 2018-12-31 | 2021-09-24 | 美国陶氏有机硅公司 | Silicones and preparation method thereof |
| KR102268923B1 (en) * | 2019-02-20 | 2021-06-24 | 주식회사 로빈첨단소재 | Method for producing surface-modified nanocellulose, and nanocellulose thereof |
| CN110373277B (en) * | 2019-07-05 | 2021-03-12 | 江西能洁化工有限公司 | Train cleaning agent |
| CN112961255B (en) * | 2021-02-23 | 2022-07-19 | 中国石油大学(华东) | Environment-friendly natural gas hydrate decomposition inhibitor and preparation method and application thereof |
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- 2008-08-22 EP EP08827625.8A patent/EP2182009B1/en not_active Not-in-force
- 2008-08-22 JP JP2009529072A patent/JP5298018B2/en not_active Expired - Fee Related
- 2008-08-22 US US12/673,914 patent/US8569263B2/en not_active Expired - Fee Related
- 2008-08-22 CN CN201210201456.5A patent/CN102746406B/en not_active Expired - Fee Related
- 2008-08-22 KR KR1020107003663A patent/KR20100044223A/en not_active Application Discontinuation
- 2008-08-22 CN CN200880103518.0A patent/CN101778868B/en not_active Expired - Fee Related
- 2008-08-22 WO PCT/JP2008/065002 patent/WO2009025354A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4137399A (en) * | 1976-10-02 | 1979-01-30 | Dynamit Nobel Aktiengesellschaft | Method of preparing functionalized celluloses |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102746406A (en) | 2012-10-24 |
| CN101778868B (en) | 2012-07-18 |
| JP5298018B2 (en) | 2013-09-25 |
| EP2182009A4 (en) | 2012-12-19 |
| EP2182009B1 (en) | 2013-11-13 |
| KR20100044223A (en) | 2010-04-29 |
| WO2009025354A1 (en) | 2009-02-26 |
| US20110218336A1 (en) | 2011-09-08 |
| JPWO2009025354A1 (en) | 2010-11-25 |
| CN101778868A (en) | 2010-07-14 |
| US8569263B2 (en) | 2013-10-29 |
| EP2182009A1 (en) | 2010-05-05 |
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Effective date of registration: 20160226 Address after: Tokyo, Japan, Japan Patentee after: LION SPECIALTY CHEMICALS CO., LTD. Address before: Tokyo, Japan, Japan, the ink area of 1, the number of the first round of the 7, No. 3 Patentee before: Lion Corporation |
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